EP0465485A4 - Procede de separation d'emulsions d'huile et d'eau. - Google Patents

Procede de separation d'emulsions d'huile et d'eau.

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Publication number
EP0465485A4
EP0465485A4 EP19900904528 EP90904528A EP0465485A4 EP 0465485 A4 EP0465485 A4 EP 0465485A4 EP 19900904528 EP19900904528 EP 19900904528 EP 90904528 A EP90904528 A EP 90904528A EP 0465485 A4 EP0465485 A4 EP 0465485A4
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EP
European Patent Office
Prior art keywords
mixture
water
oil
agent
εaid
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Granted
Application number
EP19900904528
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German (de)
English (en)
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EP0465485B1 (fr
EP0465485A1 (fr
Inventor
Ernest O Ohsol
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Quadrant Management Inc
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Individual
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/04—Breaking emulsions
    • B01D17/042—Breaking emulsions by changing the temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
    • B01D17/02—Separation of non-miscible liquids
    • B01D17/04—Breaking emulsions
    • B01D17/047—Breaking emulsions with separation aids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D21/00—Separation of suspended solid particles from liquids by sedimentation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D21/00—Separation of suspended solid particles from liquids by sedimentation
    • B01D21/01—Separation of suspended solid particles from liquids by sedimentation using flocculating agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C02F1/025—Thermal hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material

Definitions

  • the invention relates to the purification and separation of oil, water and solids from waste oil.
  • This waste oil can be found in many forms and is particularly found in large quantities as storage tank bottoms and in lagoons where waste oil has historically been transferred for storage.
  • Crude oil contains varying, but in some cases high, percentages of B.S. and W. , i.e., bottom sediment and water, plus paraffin and other materials. These contaminates adhere to,the sides and build up on the bottom of crude oil storage tanks, forming a thick, viscous slurry referred to as waste tank bottom sludge or bottom settlings and water.
  • This build-up of water, paraffin, sand, clay, and other materials is generally rich in hydrocarbon content, but unsuitable for refining.
  • tank bottom sludge is characterized by high concentrations of inorganic contaminants, e.g. , inorganic salts and heavy metals
  • U.S. Patent 2,533,166 to Jones discloses a method of producing polyacrylamides having a high peptizing action to prevent the sedimentation of finely divided materials such as pigments and silver halide dispersed in aqueous media.
  • U.S. Patent 3,025,236 to Barrett et al. shows the sodium salt of sulfonated dodecyl diphenyl oxide and an acrylamide polymer as a flocculating agent.
  • U.S. Patent 3,090,759 to Jenkins discloses the use of a homopolymerized acrylamide and certain related copolymers having a molecular weight of at least 40,000 and preferably up to one million for use in breaking oil-in-water emulsions.
  • U.S. Patent 4,519,899 to Oertle et al. describes a process and apparatus for the purification of oil using a jet pump mixer at elevated temperature.
  • the jet pump was used as a mixing device in conjunction with a static mixer.
  • the present invention provides a process and apparatus for separating oil, water and solids from emulsions. More particularly, the present invention provides a process and apparatus for continuously separating oil, water and solids from stable mixtures thereof, comprising heating the mixture to at least about 115°C, rapidly cooling the mixture to below about 100°C, separating the solids from the liquids and separating the water from the oil. Preferably, the invention also includes the step of adding a flocculant prior to cooling the mixture.
  • the invention deals with mineral oil emulsions stabilized by finely divided solid materials to be separated into an economically processable mineral oil fraction which is low in both suspended solids, water, heavy metals and other contaminants, an ecologically acceptable waste water, and, preferably, flocculated finely divided clean oil-free solids which can easily be disposed of.
  • An important feature of the invention is an unusually high temperature treatment of the sludge with suitable agents to remove the encapsulating solids from the dispersed liquid phase. This treatment is then followed by more conventional separation procedures.
  • the drawing figure illustrates an embodiment of the • invention in schematic form. It particularly shows the step of heating the mixture using superheated water and/or steam, followed by cooling the mixture by flashing it to lower pressure and separating the components of the mixture by centrifugally enhanced separation steps.
  • the emulsions to be treated are mixed with an effective amount of a surfactant or surfactants which acts as a demulsifying agent. Then, the emulsions are pressurized to an absolute pressure between 1.7 and 8 at and mixed with a sufficient quantity of superheated water and/or steam (liquid water above its normal boiling point) or superheated steam to raise the temperature of the mixture to at least about 115°C, preferably higher.
  • a surfactant or surfactants acts as a demulsifying agent.
  • the emulsions are pressurized to an absolute pressure between 1.7 and 8 at and mixed with a sufficient quantity of superheated water and/or steam (liquid water above its normal boiling point) or superheated steam to raise the temperature of the mixture to at least about 115°C, preferably higher.
  • the addition of the superheated water and/or steam to the pressurized oil mixture causes a dramatic decrease in viscosity and surface tension, aided and abetted by the presence of the surfactants which may be added before or after the hot water.
  • the components are well mixed, as for example by use of an interrupted-helix static mixer, or an in-line stirred tank.
  • a suitable amount of a flocculating agent is preferably added to the mixture, using an injecting means and a low-residence time mixing device such as the static mixer mentioned above.
  • a flocculant is particularly desirable for those emulsions in which the solids do not melt or decompose due to the increase in temperature and pressure.
  • a flocculant may be not be necessary.
  • the suspended solids are particles of hydrocarbon waxes which liquify when the temperature and pressure of the mixture is increased, so that the problem of suspended solids is eliminated without using a flocculant.
  • flocculant ⁇ When flocculant ⁇ are used, they preferably are high molecular weight polymers which are unstable at high temperatures. Therefore, means are provided for quickly contacting the sensitive flocculant with the oil-water- solid ⁇ system to be treated. After a residence time of as much as 5 minutes, but preferably less than 1 minute, the temperature of the system is rapidly dropped, in as little as 1 to 2 seconds, so as to prevent substantial deterioration of the flocculant.
  • the rapid cooling can be accomplished by suddenly releasing the pressure of the fluid, for example, by passing it through a Venturi expansion jet, or by quickly adding a substantial amount of cold water and blending it with the fluid.
  • the flocculant may be added at the throat of the Venturi expander.
  • the solids may be expeditiously removed utilizing conventional means such a ⁇ cyclone or hydrocyclone separators, screens, impingement devices, etc.
  • the expansion method for achieving the rapid cooling ha ⁇ the additional benefit of helping to rupture the micro- structure of solids protecting the oil-water interfaces, which has inhibited normal oil-water separation by settling/coagulation of droplets. — D —
  • the oil-water dispersion can much more easily be separated by conventional means such a ⁇ settling, centrifuging, pas ⁇ age through semi- permeable membrane ⁇ , etc.
  • the pre ⁇ ent proce ⁇ s is particularly useful in conjunc ⁇ tion with such waste mixtures a ⁇ have been previously considered completely untreatable but is also u ⁇ eful for more economically treating suspension-emulsions which have been more or less tractable to treatment by conventional methods.
  • the waste may contain from very thin mineral oil fractions, almost in the gasoline range, down to heavy residual oils which mu ⁇ t be heated to be flowable.
  • the solids suspended in the material are usually finely divided materials, which can include salts which are soluble in water, such a ⁇ sodium chloride, but are in larger quantity than is soluble in the water present.
  • the suspended solids may also include insoluble salts such as calcium carbonate, ferric phosphate, hydroxides, such a ⁇ ferric hydroxide, aluminum hydroxide, ⁇ ilicates, phosphates, e.g., calcium and magnesium phosphates, clays, soot, carbon and plain "dirt" which is practically anything organic or inorganic in finely divided form.
  • the finely divided particles may range from smaller colloidal sizes of the order of 0.1 microns up to and including particles which are large enough to settle when standing by gravity.
  • the nature of the emulsion-suspension is heterogeneous at best.
  • the emulsion may be of a water-in-oil or oil-in- water, or a mixture of both, and the insoluble solid par ⁇ ticles can be suspended in either the oil phase, the water phase or the interface between the phases. Finely divided solid particles in themselves may act as emulsifying agents under some conditions.
  • the emulsion-su ⁇ pen ⁇ ion mixture may have variou ⁇ type ⁇ of naturally occurring emul ⁇ ifying or suspending agents present.
  • the surfactants aid in breaking the water-in-oil and oil-in-water emulsions causing the separate coalescence of each of the oil and water particles.
  • a polyelectrolyte aids in the flocculation and separation of the finely divided solids from both the oil and water phases, as well as the interfaces.
  • the oil-water separation is greatly facilitated by first removing the fine solids. Because the emulsion suspen ⁇ ion being fed into the system is often primarily a mixture of waste streams from various sources, the composition may vary widely. Usually it contains at least about 20 percent mineral oil.
  • mineral oil refers to a mineral oil of any type, including crude oil directly as recovered from a well, or any of the streams in a petroleum refinery which may contain from almost gasoline type components down through residual still bottoms.
  • the emulsion suspen ⁇ ion from such a source usually contains at least about 5 percent water. However, the composition may contain up to about 80 percent of water.
  • the water may be from almost a salt-free water to one which is essentially salt saturated. Under many condition ⁇ , the water re ⁇ ult ⁇ from the influx of sea water or is a residual water layer in which some sea water salts and other salts have been dis ⁇ olved so that the aqueous phase may be nearly saturated in sea water salts as well a ⁇ many other component ⁇ . Water may have been evaporated off, which increases the salts concentrations.
  • the oil may be from a water flooding petroleum recovery operation of an oil field.
  • incoming mineral oil is run through distillation processes to separate out desirable fraction ⁇ which may be fed to thermal or catalytic crackers, or other refinery processes, with the salt ⁇ and insolubles and residual water being concentrated in the rejected fractions so that the intractable fractions from all over a refinery may be fed to the present system for treatment.
  • desirable fraction ⁇ may be fed to thermal or catalytic crackers, or other refinery processes, with the salt ⁇ and insolubles and residual water being concentrated in the rejected fractions so that the intractable fractions from all over a refinery may be fed to the present system for treatment.
  • the solid materials may be only a fraction of 1 percent up to about 40 percent by weight or more especially if the waste ha ⁇ been stored in lagoons.
  • the waste oil can be converted into high quality oil which may be added to a refinery stream who ⁇ e • composition it most nearly resembles for distillation, cracking, hydrogenation, desulfurization, or other proces ⁇ ing to obtain economically useful products including gasoline, lubricating oil, heating oil, residual fuel oil and the like.
  • the water and solids are also recovered, in a form suitable for non-polluting disposal.
  • An agitator 3 and a ⁇ team heating coil 4 serve this purpose.
  • the sludge entering the mixer is preferably at a pres ⁇ ure of at least 7 atmospheres gauge, 8 atmospheres absolute, and is joined by steam and/or hot water coming through line 8 from a water heater 6 at a corresponding pressure.
  • the water will have been heated by gas combusted in burner 7, pas ⁇ ing through ⁇ uitable heat exchange surfaces in 6 and the flue gas then exiting through duct 9.
  • the water temperature will correspond to its boiling point at the given pres ⁇ ure i.e., at 7 atmospheres gauge, approximately 170°C.
  • the water and the sludge are thoroughly blended in mixer 10, and before exiting the mixer, suitable amounts of demulsifying or separating agents are continuously injected from vessel ⁇ 15 and 16 via proportioning pump ⁇ 12 and 14 and lines 11 and 13.
  • Treating agent A from ves ⁇ el 15 may be a surfactant or surface tension lessening agent such as a polyethylene oxide-alkyl phenol condensation product, non-ionic in character
  • treating agent B from vessel 16 may be flocculating agent such as a polyacrylamide or modified polyacrylamide or derivative thereof, cationic in character.
  • the amounts u ⁇ ed may, for example, be 0.005 weight percent to 0.05 weight percent ba ⁇ ed on the entering sludge.
  • a third treating agent C may be added a ⁇ the mixture is leaving the mixer and entering nozzle 20 where the pre ⁇ sure is substantially reduced.
  • Thi ⁇ third agent enter ⁇ from ves ⁇ el 17 via proportioning pump 18 and injection line 19.
  • Agent C may be a complexing agent ⁇ uch as citric acid, glycolic acid or EDTA, the purpose of which i ⁇ to sequester metal contaminants contained in the oil and bring them out into the water phase.
  • Agent C will also be added in suitably small amounts in the range of 50 to 500 parts per million.
  • Agent C it may be preferable to inject Agent C at the place shown for Agent B, and Agent B at the place shown for Agent C - for example, if Agent B is very heat sensitive flocculating agent and if Agent C requires a longer contact time to be effective.
  • the now blended mixture of sludge, hot water and treating agents pas ⁇ e ⁇ through a nozzle 20 which may be of the Venturi type, dropping the pre ⁇ sure to just a few or even le ⁇ than one atmosphere gauge, e.g. 0.3 to 0.6, atmospheres gauge, and thereby allowing a portion of the contained water to flash into steam, and dropping the temperature to the corresponding boiling point of water (109 to 115°C) .
  • the amount of water thus vaporized is surpri ⁇ ingly small, of the order of 1 to 8 percent of the contained liquid water, but i ⁇ enough to multiply the volume of the fluid a ⁇ it enter ⁇ a fla ⁇ h drum 21 by many fold.
  • the fluid enter ⁇ the fla ⁇ h drum 21 tangentially at the upper third of the vessel to facilitate disengagement of vapors from the liquid-solid slurry.
  • the vapors will be mainly steam, but also will include small amounts of volatile material vaporized from the sludge, which may include H 2 S, mercaptan ⁇ , COS, disulfide ⁇ , and nitrogen compounds in addition to low-boiling hydrocarbon ⁇ . Due to the unplea ⁇ ant odor and possible toxicity of some of these volatile contaminants, there is provided a small scrubber 23 for the vapors leaving 21 through line 22.
  • the scrubber may be a vertical drum with Raschig ring or Berle saddle packing fed with a suitable scrubbing liquid such as a 10 percent NaOH solution in water, through line 24 and issuing through line 25, to be circulated. Very little of the steam will condense into the scrubbing liquid, and non- toxic steam vapors will, issue from the scrubber through line 26, suitable for heating purposes.
  • a suitable scrubbing liquid such as a 10 percent NaOH solution in water
  • the ⁇ olid-liquid mixture remaining after the flashing step is ⁇ ue ⁇ through line 27 into a hydrocyclone 28.
  • This i ⁇ a ⁇ mall diameter cyclone type ⁇ eparator, the feed material entering tangentially near the top.
  • Solid ⁇ are ⁇ eparated due to the high speed rotation and con ⁇ equent centrifugal force generated in the liquid, and leave at the conical bottom, while the remaining liquid exit ⁇ from the center at the top. Solids separation is facilitated due to breakup of the occluding structures which occurs in the flashing step and due to the surface tension modifying effects of the agents added prior to flashing.
  • the solid ⁇ leaving hydrocyclone 28 are joined by a ⁇ tream of recycled hot water from line 33 and pa ⁇ via line 32 into a second hydrocyclone 29.
  • the recycled hot water serves to rinse the separated solids free of oily material.
  • additional detergent material F may be added with this rin ⁇ e water, or a plurality of such hydrocyclone ⁇ in series may be provided for a countercurrent solids washing system. In the drawing only one such wash hydrocyclone i ⁇ > shown.
  • the washed solids separate and exit from 29 through line 34 and drop onto vibrating screen 35.
  • the solids are shaken free of adhering liquid and exit at 37, dropping into a receiving vessel such as a "Dumpster" for easy disposal a ⁇ non-polluting, oil-free solid material.
  • a stream of hot air,or flue gas from the water heater may be blown across the vibrating screen.
  • the spent rinse water issuing from the top of hydrocyclone 29 via line 31 is recycled to the first hydrocyclone 28, optionally with the addition of the above- mentioned detergent at F.
  • guard filter 40 which may be a cartridge or Cuno type filter. Solids periodically removed from it are added to the solids entering the screen 35.
  • the liquid stream leaving guard filter 40 is fed directly to a continuous centrifuge 42. This is an axial flow machine of high throughout capacity, developing a separation force over 1000 times gravity. Oil leaves the machine through line 45, passes through SELAS separator 46 via line 72 to receiver 73.
  • the SELAS separator contains a semi-permeable membrane which collects and removes traces of water which might remain as a haze in the oil. The oil reaching receiver 73 i ⁇ essentially water-free and clear.
  • the removed water leaves the separator through line 48 and is returned to the centrifuge.
  • Water removed from the solids via the vibrating screen can also be added to the feed to the centrifuge via line 38 (or to the feed to filter 40 if there are any traces of solids in the water) .
  • the separated oil returns to the centrifuge via line 44 while the clear water continues on via line 50 to a water purification system.
  • water treating agent D from container 57 is added via metering pump 55 and feeder line 53 to the water entering static mixer 51 via line 59.
  • Treating Agent D may be a polyvalent cationic material such as alum or ferric chloride, added in amounts of 0.01 to 0.2 percent on the water being treated.
  • a precipitating agent E from container 58 is added via metering pump 56 and feeder line 54 to line 60.
  • Agent E may be a solution of sodium hydroxide or of sodium carbonate, for example.
  • the static mixers are of similar type to static mixer 10 described previously.
  • a holding tank 61 is provided to allow sufficient time for the precipitated treating " Agent D to flocculate, thereby removing impurities from the water stream.
  • additional treating agents may be added, ⁇ uch a ⁇ suitable small amounts of H2S, SO 2 or activated carbon.
  • the thus removed contaminants, incorporated in the precipitated flocculating agent are now removed in filter 63, fed by line 62.
  • the liquid is released through line 65 into clean water receiver 66.
  • the filter may be a dual cartridge type filter or a rotary filter or a Kelly filter. It i ⁇ desirable to keep the water system enclosed so as to conserve heat, since most of the water i ⁇ recycled to heater 6 via line 69, pump 70 and line 71. Pump 70 should, of course, repre ⁇ surize the water enough to enter heater 6.
  • Any chelated metals are pre ⁇ ent in the aqueou ⁇ phase and can be precipitated in a later step using pH adjustment and precipitation.
  • Demul- sifying agents may include oil soluble or water soluble surface active agents.
  • sulfo ⁇ uccinate ⁇ such a ⁇ ⁇ odium • di (tridecyl) ⁇ ulfo ⁇ uccinate, sodium di(hexyl)- sulfo ⁇ uccinate, di(sodium polyoxyethanol)-sulfosuccinate and the various grades of sodium di(2- ethylhexyl) ⁇ ulfo ⁇ uccinate.
  • Thi ⁇ last material is sold by American Cyanamid Company under the trademark Aerosol OT and is one of the first of the synthetic surface active agents.
  • a pharmaceutical grade of sodium di(2-ethyl- hexyl) sulfosuccinate is available, and i ⁇ u ⁇ ed as a fecal softener, its toxicity is minimal.
  • Other useful oil soluble ⁇ urface active agents include, for example, sodium or calcium petroleum sulfonate ⁇ , ⁇ ulfonated or ⁇ ulfated ca ⁇ tor oil, ⁇ ulfonated or ⁇ ulfated tallow, ⁇ ulfated or ⁇ ulfonated oleic acid, and ⁇ ulfonated or ⁇ ulfated soybean oil.
  • preferentially water soluble surface active agents are sodium isopropylnaphthalene sulfonate, other alkyl aryl ⁇ ulfonates, e.g. sodium decylbenzene sulfonate mixed octyldecyla ine octyldecylguandine-polyoxyethanol, and others obtained under a wide variety of trade designation ⁇ in the indu ⁇ try.
  • the ⁇ e include sodium dodecylbenzene sulfonate, stearamidopropyldimethyl- ⁇ - hydroxyethyl ammonium nitrate, tall oil ethoxyethylate with from about 6 to 15 mole ⁇ of ethylene oxide, ⁇ odium lauryl ⁇ ulfate, sodium octadecyl sulfate, sodium alkyl sulfate ⁇ from alpha olefins, or from oxoprocess alcohols.
  • Nonyl phenol if ethoxylated with about 9.5 moles of ethylene oxide i ⁇ both water and oil ⁇ oluble, and by changing the degree of ethoxylation can be modified to either the oil or water ⁇ ide.
  • These surfactants may include for example polyethylene oxide, polypropylene oxide and copolymers phenol adducts thereof either random or block.
  • These surfactant ⁇ may al ⁇ o be functionalized with organic acids or esters for example ethyl acrylate, styrene sulfonate e ⁇ ter, etc.
  • high molecular weight material ⁇ ⁇ uch as polyacrylamides are preferred.
  • One grade of polyacrylamide of about 15 million molecular weight and less than one percent hydrolysis is conveniently obtainable on the commercial market. Potable water grades are available. This product, with a low residual monomer content is acceptable for the treatment of drinking water.
  • copolymer ⁇ of acrylamide with acrylic acid, and aminated acrylate ⁇ such as tho ⁇ e derived from monomethyl amine-epichlorohydrin, quaternized monomethylamine- eipchlorohydrin, ethylene diamine dimethylamine- epichlorohydrin, dimethylamine reacted with polyacrylamide may be con ⁇ idered u ⁇ eful.
  • a preferred polyacrylamide flocculating agent contains up to 20% by weight of a quartermized dimethylaminoethyl acrylate copolymerized with the polyacrylamide.
  • Surfactant ⁇ may be added at any time before or during the mixing ⁇ tep ⁇ , however, it i ⁇ preferred that surface active agents be added first and remain at a high temperature with mixing for a longer time.
  • More expensive les ⁇ ⁇ table flocculating agents e.g. polyacrylamides, may be added at a point in the process such that the residence time of the surfactant at the higher temperature is minimized.
  • the amount of flocculating agent or agents added will vary widely depending upon the agents themselves and the particular composition but will generally be an amount effective to form floes of sub ⁇ tantially all remaining ⁇ olid particle ⁇ of sizes of from about 20 microns to less than 2 microns in diameter. It is preferable that the amount of flocculating agent added be sufficient to form floes that will be retained on a 200 mesh sieve (Tyler Sieve Series).
  • Dispersion of the polymers is preferably accomplished by the application of a dilute solution of the polymer to the fluid to be treated.
  • Some of the most effective flocculating agents for facilitating separation of solids from oils, water or oil- water mixture ⁇ are high molecular weight functional polymers ⁇ uch a ⁇ polyacrylamide, certain polyacrylate ⁇ and protein-like material ⁇ .
  • the ⁇ e compound ⁇ are, however, temperature ⁇ en ⁇ itive, and tend to break down in molecular weight or lo ⁇ e effective functionality upon expo ⁇ ure to heat.
  • the invention allows the beneficial effects of these desirable flocculants to be retained even while u ⁇ ing them at high temperatures by limiting the time of exposure to a very short interval, between the time of mixing the subject emulsion with pressurized hot water to the time of expansion or "flashing" through a nozzle.
  • This time may be a ⁇ ⁇ hort as a few tenths of a second.
  • high temperature say 110-170°C
  • the temperature drop during expansion can be over 100°C under certain practical condition ⁇ .
  • part of the water is vaporized, and under practical conditions the volume may increase many fold with only minor fraction of 1 to 10 percent vaporizing.
  • the expansion in addition to providing the desired cooling effect, also ensure ⁇ that the ⁇ olid "structure" surrounding each droplet of the emulsion is ruptured and destroyed, thus facilitating the three-phase separation which ensues rapidly following the expansion.
  • the solids are first removed, as soon as pos ⁇ ible, and then the oil-water ⁇ eparation can be made, no longer inhibited by the pre ⁇ ence of ⁇ olid "structures" around the droplets.
  • the oil mixture may be treated with a metal complex-forming compound in the presence of a surfactant in order to isolate any heavy metals present in the oil mixture.
  • the complexing agents used are aqueous solution ⁇ of inorganic or organic acid ⁇ , as described in, for example British Patent No.
  • 1,329,174 as well as polycarboxylic acids and/or polyaminocarboxylic acids (cf. U.S. Patent No. 3,838,102) or other chelating agents, such as nitrilotri- acetic acid and its ⁇ odium salts or ethylenediaminetetra- acetic acid and its sodium salt ⁇ (Na3-EDTA) (cf. U.S. Patent No. 3,951,917), the latter al ⁇ o in combination with quater ⁇ nary ammonium salt ⁇ (U.S. Patent No. 4,026,870), ⁇ uch as complex-forming agents from the group comprising the bis- guanide ⁇ (cf. U.S. Patent No.
  • chelating agent ⁇ include citric acid, glycolic acid, pho ⁇ phoric acid derivatives, phthalodinitrile and the like.
  • the complex-forming agent is preferably present in an amount of from 0.5 to 5 moles per mole of metal ion in the oil.
  • concentrations from about 30 to about 10,000 parts per million are preferred.
  • Suitable mixers include, for example, static mixers of the orifice-pipe type, high shear rotating plate types, interrupted helix types or merely a stirred tank.
  • Filters may be used to clean the initial feed stream or at any point throughout the process.
  • the filters used may be any of those known in the art for example screen or grid type filters which may be self-cleaning or periodically purged, or leaf filters or drum filters.
  • Process hot water and steam may be supplied by, for example, a gas fired boiler.
  • Preheating the waste oil may be neces ⁇ ary for very high vi ⁇ co ⁇ ity ⁇ ludge ⁇ .
  • Preheating the wa ⁇ te oil may be accomplished by any heating means known in the art.
  • the waste oil may be preheated using a steam coil, an electrically heated coil, direct addition of steam, addition of microwave energy infrared energy or any other convenient means.
  • the wa ⁇ te oil can be filtered or ⁇ trained to remove debri ⁇ and large ⁇ ediment, prior to the actual treating process described above.
  • the cooling means can be any convenient means known in the art, for example, heat exchange with the cooler, feed stream or cold water or air or by the addition of cold water to the stream.
  • a preferred cooling means may involves flashing the high pres ⁇ ure, high temperature mixture into a lower pre ⁇ ure ve ⁇ el through an orifice or venturi. By using a flashing step the mixture can be cooled 50°C to 100°C almost instantaneously.
  • the volume of the mixture can be increased tenfold with a corresponding evaporation of about 3 percent of the aqueous phase and a decrease in temperature of about 60°C.
  • the ⁇ olid ⁇ must be removed from the mixture to prevent them from re-establishing the su ⁇ pen ⁇ ion matrix.
  • Solids derived from the process may be washed with hot water or steam.
  • Separation of the flocculated mixture can be achieved by passage through a centrifuge. Conveniently the solids are separated first, then the two liquid phases are separated in a subsequent stage.
  • the organic phase may be further cleaned by further centrifugation or filtering or by using a SELAS type liquid separator.
  • Additional chemical agents for example, chelating agents, may be added immediately upstream from the cooling or flashing ⁇ tep.
  • the liquid in the receiver was promptly centrifuged in a heated centrifuge to separate oil and water layers.
  • the centrifugation product wa ⁇ found to be two di ⁇ tinct layer ⁇ , the upper layer containing 139.5 grams of 30°C API gravity oil. It was slightly cloudy, but upon pas ⁇ ing through a SELAS TM ⁇ eparator wa ⁇ clear and free of droplet ⁇ .
  • a SELAS separator is a commercial semi-permeable membrane device for removing ⁇ mall traces of water from oil, or of oil from water.
  • Example 1 The sludge was preheated as in Example 1 to about 70° and then blended with 160 grams of water preheated to 170° in an autoclave, as in Example 1.
  • the autoclave wa ⁇ carefully vented from the vapor ⁇ pace and the liquid- ⁇ olid mixture then di ⁇ charged through a filter ⁇ creen of 240 me ⁇ h ⁇ ize.
  • the ⁇ olids were wa ⁇ hed with boiling water, the washings being added to the filtrate.
  • the solids collected on the screen were dried and weighed and found to be 16.5 grams, substantially oil-free.
  • the filtrate wa ⁇ promptly centrifuged to yield two distinct layers, an upper oil layer of 135.6 grams, only slightly cloudy, and a lower water layer of 192 gram ⁇ , containing a ⁇ light haze of mud and oil.
  • the water layer after agitation with 5 gram ⁇ of alum and 2.5 gram ⁇ of sodium carbonate, each dissolved in a minimum amount of water, allowing 10 minutes settling time, wa ⁇ filtered through filter paper.
  • the effluent water was clear and free of oil.
  • the oil layer was passed through a water-repellant membrane filter of the SELAS Separator type, and emerged free of water or solids.
  • EXAMPLE 3 1500 grams per hour of the heated and stirred sludge of Example 2 is fed by means of a progressive cavity pump ("MOYNO” type) to a continuous mixing line of three half- inch diameter static mixers in series (“KENICS” type) .
  • the stream of sludge was joined by a stream of water under a pres ⁇ ure of 900 kilopascals absolute (116 psi gauge) and about 175°C flowing at a rate of 1400 gram ⁇ per hour.
  • WISK TM liquid detergent a commercial combination of anionic and non-ionic surfactants
  • the liquid collecting in the bottom of the chamber was allowed to discharge through a fine screen to remove solids, and passed at atmospheric pre ⁇ sure into a continuous vertical centrifuge to separate an oil phase from a water phase. Traces of solids were also discharged from the continuous centrifuge by means of a small helical conveying device at the bottom.
  • the centrifuge was operated at a speed of rotation to give a force of approximately 2000 times gravity.
  • the initial sludge contained 600 ppm of vanadium metal (mostly held in the oil phase a ⁇ organic adducts) .
  • the recovered water upon treatment with ferric chloride and sodium hydroxide, wa ⁇ filtered; most of the vanadium was found in the filter cake; and the water thus purified contained only 2 ppm of vanadium.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Physics & Mathematics (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un procédé et un appareil de séparation d'huile, d'eau et de solides d'émulsions. Plus particulièrement l'invention concerne un procédé ainsi qu'un appareil de séparation continue d'huile, d'eau et de solides d'émulsions. Plus particulièrement l'invention concerne un procédé ainsi qu'un appareil de séparation continue d'huile, d'eau et de solides de mélanges stables de ceux-ci, consistant à chauffer le mélange à au moins environ 115°C, à refroidir rapidement le mélange en dessous de 100°C, à séparer les solides des liquides et à séparer l'eau de l'huile. L'invention comprend également de préférence l'étape consistant à ajouter un floculant avant le refroidissement du mélange.
EP90904528A 1989-03-02 1990-03-02 Procede de separation d'emulsions d'huile et d'eau Expired - Lifetime EP0465485B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US07/318,176 US4938876A (en) 1989-03-02 1989-03-02 Method for separating oil and water emulsions
US318176 1989-03-02
PCT/US1990/001079 WO1990009833A1 (fr) 1989-03-02 1990-03-02 Procede de separation d'emulsions d'huile et d'eau

Publications (3)

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EP0465485A4 true EP0465485A4 (fr) 1991-11-08
EP0465485A1 EP0465485A1 (fr) 1992-01-15
EP0465485B1 EP0465485B1 (fr) 1994-09-28

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EP (1) EP0465485B1 (fr)
JP (1) JP2962821B2 (fr)
CA (1) CA2048635C (fr)
DE (1) DE69012988T2 (fr)
ES (1) ES2064724T3 (fr)
WO (1) WO1990009833A1 (fr)

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Also Published As

Publication number Publication date
DE69012988D1 (de) 1994-11-03
EP0465485B1 (fr) 1994-09-28
DE69012988T2 (de) 1995-05-11
CA2048635A1 (fr) 1990-09-03
JPH05504714A (ja) 1993-07-22
US4938876A (en) 1990-07-03
EP0465485A1 (fr) 1992-01-15
ES2064724T3 (es) 1995-02-01
WO1990009833A1 (fr) 1990-09-07
CA2048635C (fr) 1996-07-30
JP2962821B2 (ja) 1999-10-12

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